Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
-1- 2~'~227~
ir~~r~,~~d M~,~h~d ~f A~~i ietai C~~tina~s ~n_
~~bic ~~r~n Nitride and Articles ade_Therefr~rr_i
The present invention is gen~rally related to a method of
applying metal coating on cubic boron nitride. More particularly, the
invention relates to coating electroless metal alloys on cubic boron
nitride.
1 5 Cubic boron nitride is extremely hard having a ~/ickers
hardness of about 5000. Its hardness makes cubic boron nitride
useful in a variety of industrial components.
Abrasiv~ particles, such as cubic boron nitride particles,
have been extensively used for cutting, grinding, lapping and
polishing in metal removing industries as well as in medics! fields
such as dentistry and surgery. Abrasive particles are used in
abrasive tools such as grinding and dres~>ing wheels, crowns and
single point tools. Considerable aimount of research has gone into
improving the bonding properties of cubic boron nitride to th~
2 5 matrices of these tools since poor bonding at th~ cubic boron
nitride/matrix interface leads to dislodgement of the cubic boron
nitride particl~ from the matrix during the abrading operation. As a
result of this research, it is known in the art that the m~tal coating
of abrasive particles improves the retention of such particles in the
3 0 matrices of various abrasive tools, such as resin bonded wheels. In
particular it is known that the retention of cubic boron nitride
particles is improved with nickel coating. To improve the retention
of cubic boron nitride particles, their surfaces ar~ provided with a
rough textur~d nickel coat having jagged edges. The jagged edges
3 5 provide the metal coated particles improv~d mechanical interlocking
means with which to retain them in the resin matrix during the
2 ~ ~~ ~ ~ ,~ ~~ R~-21,493
abrading operation. The metal coat also prove es means for evenly
transfering heat generated along the surfaces of the abrasiv~
particles during the abrading action. However metal layers have
poor adhesion to cubic boron nitride.
it is also known in the art that the retention of cubic
boron nitrides in the abrasive tools is further improved by providing
the particles with multiple layers of metals, such as molybdenum,
titanium, niobium, chromium, zirconium, copper and nickel.
The metal coating of the particles may be achieved by a
variety of methods depending on the nature of the mete! coating.
The metal coating may be applied under high temperatur~, by well
known processes, such as chemical vapor deposition, molten salt
deposition and powder agglomeration coating. The main drawback of
such techniques is that the high process temperatures can
significantly degrade the abrasive particles. The aforementioned
problem of degradation may b~ somewhat obviated by
electrolytically,' electrolessly or vacuum depositing the metal
coating on abrasive particles, however the problem of poor adhesion
to cubic boron nitride still remains.
The present invention is directed to improving adhesion
of metal coats to the surfaces of cubic boron nitride particles.
The present invention is directed to a method of
improving adhesion of a nickel alloy coat too a surface of a cubic
boron nitride article comprising the steps of contacting said article
for an effective time with an electroless plating bath for plating
said surface of said article to a desired thickness, said bath
comprising a compound of nickel and a compound of an element
selected from the group consisting of boron, molybdenum, titanium,
niobium and chromium, gradually heating the electrolessly plated
article in a non~oxidizing atmosphere from a first temperature to a
desired heat treatment temperature at a predetermined rate, and
maintaining the electrolessly plated article at the desired heat
E~p~21,4.93
treatment temperature until a desired degree of adhesion between
the surface and the metal alloy coat is attained.
Typically a nickel/boron alloy coat is applied by the
aforementioned method to cubic boron nitride particles. laid
particles are then uniformly dispersed and embedded in a resinous
matrix of a grinding wheel to improve its abrasion efficiency.
~ther advantages of the invention will become apparent
upon reading the following detailed description and appended claims.
The present invention is directed to improving adhesion
of metal coatings on cubic boron nitride surfaces. The cubic boron
nitride surfaces are electrolessly plated with a nickel alloy
containing a metalloid, such as boron, or a transition metal, such as
1 5 molybdenum, titanium, niobium or chromium, to improve the
wettability of the the cubic boron nitride surfaces as wail as
improve formation of a chemical bond between the nickel alloy and
cubic boron nitride.
~eneraily an adhesive bond between the metal layer and
the surface of the underlying substrate is ~stablished by interfacial
molecular contact between the metal layer and the surface. The
interfacial molecular contact is proportional to the wettabiiity of
the surface. The wettability of the surface is defined in terms of
the angh of contact of a liquid droplet on a surfac~. A wettable
surface will have acute angle (less than 90~) of contact whereas a
non-wettable surface will have obtuse angle (more than 90~) of
contact.
Th~ st~ps of the invention provide for chemically
modifying a surface of an article of cubic boron nitride, such as
3 0 cubic boron nitride particles, for improving adhesion of a metal
layer thereon. In one of its embodiments, the process of this
invention provides for sequentially contacting the surface with the
solutions disclosed hereinafter.
2~~~2r~
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The cubic baron nitride surface is catalyticaliy activated
to permit electroless metal deposition. The catalytically activated
surface is then electrolessly plated with a metal layer of a desired
thickness. In subsequent steps the electrolessly plated surface may
be electralytically plated (electroplated) or electrolessly plated
with another layer of a metal similar to the one underneath or a
different one. The steps are normally interposed with rinsing steps.
The term "surface" ar "cubic boron nitride surface" means
a surface of a cubic boron nitride substrate used in an article such as
1 0 abrasive particles embedded in ~ grinding wheel. Typically the
abrasive particles made from cubic boron nitride have a mesh size
between 320 and 30. However it is apparent to those skilled in the
art that the present invention is also suitable for mesh sizes bigger
or smaller than those mentioned above.
1 5 if necessary the cubic boron nitride surface may be
initially degreased with a degreasing agent such as a detergent, a
suitable organic solvent or a dilute acid. Typical surface cleaners
suitable for the cubic boron nitride surface are solvents such as
Freon~ TF 1,1,2-trichiorotrifluoroethane, dilute nitric said ar dilute
2 0 hydrochloric acid. Wowever environmentally safe cleaners such as
Shipley Acid Cleaner 1113, Micro manufactured by International
Products Inc., Trenton, tdew Jersey, or alcoholic solutions of amines
such as SP-734 manufactured by Chemical Solvents Inc., Cleveland,
Ohio are often preferred.
2 5 As used hereinafter, the term "degreased" means a cubic
boron nitride substrate having its surface free of oil, finger prints
or extraneous material.
As used hereinafter "effective tim~, temperature and
concentration " relate to a period of duration, degree of temperature
3 0 and concentration respectively required to achieve a sufficient level
of the metal deposition necessary to produce a desired result on the
surface and those skilled in the art will readily realize that by
manipulating the concentrations and the temperatures of the various
aforementioned reagents used in the present invention, the time of
3 5 contact may be optimized far particular processing conditions.
-5- 2~~~~~~ RD-21,493
It is often useful to begin the activation of the surface
by treatment with an additive which aids in absorption of the
plating catalyst. Such additives are well-known in the art.
Exemplary aids to catalyst absorption include Shipley Cuposit~
1175A Cleaner-Conditioner, a mix of ethanolamine and
triethanolamine manufactured by the Shipley Company, and Metex~
9420, a product of the MacDermid Corporation.
Immersion in about 0.1°/A to about 5°/~ by volume of either
of these agents in water for about 1 minute to about 10 minutes at a
temperature of from about 40°C to about 60°C is usually
sufficient.
Preferably a Shipley Cupasit~ 1175A bath maintained at about 55~C
and having a concentration level recommended by the manufacturer,
of about 2.5% by volume, is used.
Activation of the surface far plating purposes can be
1 5 achieved by well known methods of the art. Far example, the
substrate may be contacted with an acid solution of a precious
metal, such as palladium chloride in hydrochloric acid, far a period
of time sufficient to cause catalytic activation of the surface.
One illustrative activation technique involves immersing
the surface in a solution of IVIacDermid~ D34C I'd, a product of the
MacDermid Corporation. This solution provides a palladium/tin
plating catalyst. A water rinse generally follows the activation .
step.
After surface activation and rinsing, electroless plating
2 5 of a nickel alloy coat can be undertaken. A preferred electroless
bath of the invention is an aqueous solution c~mprising a nickel salt,
a chelating agent, a reducing agent and a pH adjuster. The nicks!
salt, such as nick~! sulfate, nickel acetate or nickel halide may b~
used as a source of nickel ions. Nickel sulfate is preferred. In
3 0 general, the nickel salt should be added in an amount ranging from
about 0.01 M to about 0.2M, preferably about 0.112AA to about 0.916M,
and mast preferably about 0.114!1A. A chelating agent, such as malic
acid, acetic acid, lactic acid ar citric acid, may be used. 4Vlalic acid
is preferred. In general, the chelating agent should be added in an
3 5 amount ranging from about 0.03M to about 0.6M, preferably about
0.325M to about 0.346M, and mast preferably about 0.337dv1. The
CA 02072274 2002-04-03
RD-21,493
-6-
reducing agent, such as dimethylamine borane, alkali metal borohydride or
trimethylamine borane, may be used as a source for boron ions.
Dimethylamine borane is preferred. In general, the reducing agent should
be added in an amount ranging from about 0.005M to about 0.1 M,
s preferably about 0.04M to about 0.08M, and most preferably about 0.06M.
A pH adjuster, such as ammonium hydroxide or alkali metal hydroxide, may
be used for increasing the pH of the electroless bath. Ammonium
hydroxide is preferred. In general, the pH adjuster should be added to
maintain the pH from about 4 to about 6, preferably about 5.5.
~o Another electroless bath suitable for the present invention
comprises a conventional electroless nickel/phosphorus plating bath, such
as AK 1000~ sold by Allied Kelite Corporation, mixed with a compound of a
transitional element. The pH of the bath is adjusted from about 9 to about
10, preferably to about 9.5, by adding an alkali metal hydroxide. NaOH is
preferred. Illustrative nickel alloys used to form the metal coat include
elements, such as molybdenum, tungsten, titanium, niobium or chromium.
Molybdenum is preferred. In general, the compound of the transitional
element is added to the conventional nickel/phosphorus bath, such as AK
1000~, at a concentration of about 0.001 M to about 0.100 M, preferably at
ao a concentration of about 0.01 M to about 0.02 M. Sodium molybdate is
preferred.
Electroless baths are well-known in the art and are generally
described in the Kirk-Othmer Encyclopedia of Chemical Technoloav, 3rd
Edition, Volume 8.
25 The selection of a particular bath or electroless plating
process is not critical to the present invention. The contents of the
bath and the particular plating parameters, e.g., temperature, pH,
and immersion time, will of course depend on the particular metal
alloy being deposited thereon. Immersion times, bath temperatures,
3o and other operating parameters can be determined and controlled
according to manufacturers' suggestions. Typically the bath may be
agitated by ultrasonic or stirring means during the plating of the
cubic boron nitride particles to prevent bridging between the
-'- ~~~~w~~ RD-21,493
individual particles. A fluidized bed may be also employed to
prevent the aforementioned bridging action. Those having ordinary
skill in the plating art will be able to determine the most
appropriate plating procedure for a particular situation.
The metal coated cubic boron nitride surface is then
subjected to a heat treatment after electroless deposition of the
mete! alloy. puring the heat treatment the temperature is gradually
increased at a steady predetermined rate from a first temperature
to a heat treatment temperature for preventing balling of the mete!
1 0 layer. The term "balling" is defined as a delamination of a metal
coat from an underlying surface wherein the metal coat curls away
from the surface to form a ball-like shape. The temperature is
raised at the rate of less than 200C per minute, preferably at the
rate of about lOnC per minut~. The first temperature is typically
1 5 room temperature of about 240C. The heat treatment is conducted in
a non-oxidizing atmosphere containing an inert gas mixed with about
5 % t0 about 10 % by volume of hydrogen. The inert gas may be
selected from the noble gases of Croup XVlil of the periodic chart.
Argon is preferred. Oven heating of the entire article, i.e., substrate
2 0 with metal thereon, is sufficient, although any heating method is
suitable. Typically, this heat treatment is carried out at a heat
treatment temperature ranging from about 400~C t~ about 900aC,
preferably at about 500~C to about 700oC, for about 25 minutes to
about 120 minutes, with higher temperatures within the above range
2 5 generally compensating for shorter duration, and vice versa. The
preferred duration for the aforementioned heat treatment is about
one hour. Although the mechanism is not fully understood, the heat
treatment appears to improve formation of th~ chemical bond
between the cubic boron nitride surface and the metal layer.
3 0 If another layer of metal is to be applied an the
electrolessly metal coated surface, e.g., by electroplating, the
above-described heat treatment can in some instances be omitted if
the afarementioned heat treatment is employed after the final
plating step, as described below. However, preferred embodiments
3 5 include the heat treatment prior to deposition of the additional
metal layers.
CA 02072274 2002-04-03
RD-21,493
_g_
Though electroless plating is the preferred application method
for the second metal layer, electroplating may be also used. The substrate
is usually cleaned prior to immersion in the electroplating bath. The
cleaning can be performed by rinsing the substrate with a dilute solution of
s a strong acid, such as 10% by volume hydrochloric acid in water.
Electroplating baths are well-known in the art and are
described, for example, in U.S. Patent 4,555,315, although the particular
electroplating bath used is not critical to the present invention. The choice
of course depends in part on the particular metal being deposited. Suitable
metals include nickel, copper, cobalt, palladium, and platinum.
Furthermore, those skilled in the art appreciate that the particular bath
contents will depend upon some of the factors considered for the
electroless deposition of metal described above. A description of baths for
plating copper or various other metals is given in the Kirk-Othmer
reference described above, in Vol. 8, beginning on page 826. Baths used
to apply a layer typically include an aqueous acidic copper electrolyte such
as those of the acidic copper sulfate or acidic copper fluoroborate type;
halide ions, such as chloride and/or bromide ions; and various other
components well known in the art. The thickness of this second metal
ao layer will of course depend upon the desired end use of the metal-coated
su bstrate.
An etching agent is often used prior to the deposition of this
second electrolytic layer. A typical example of the etching agent is a dilute
solution of a strong acid, such as hydrochloric acid in water at a
as concentration of 50% by volume. The substrate is immersed in the
aforementioned etching agent for about 10 seconds to about 120 seconds.
A deionized water rinse step usually follows the etching step. The substrate
is now ready for further plating. The electrolytic bath for the second
electrolytic layer can be one of the conventional baths known in the art.
3o After deposition of the second electrolytic layer, the
surface is rinsed again with water and may be provided with a
second heat treatment for further enhancing adhesion of the metal
layers to the substrate. A typical heat treatment for this step
_g_ ~d~~2~~ Rp_21,493
involves temperatures ranging from about 100~C to about 500~C for
a time period ranging from abaut 5 minutes to about 20 hours.
In tho preferred embodiments, an article prepared by the
method of this invention usually has a first electrolessly applied
metal coat of about 0.25 micron to about 3 microns thickness; a
second electrolessly applied metal layer of about 5 microns; and a
third, if so desired, electrolessly applied metal layer of about 5
microns thickness. o-4owever it should be noted that the present
invention contemplates multiple layers of different metals and it
1 0 should not be construed that the invention is restricted to just three
or less metal layers or to specific metal layers disclosed herein.
An article prepared by the method of this invention
comprises a cubic boron nitride surface having a metal alloy layer,
such as a nickel alloy gayer, thereon. The metal is alloyed with a
1 5 metalloid, such as boron or a transitional metal, such as
molybdenum, tungsten, titanium, niobium or ohromium. The metal
alloy layer comprises an electrolessfy applied first metal coat on
the cubic boron nitride surface. Additional secondary metal layers
may be electrolessiy or electrolytically applied on top of the first
20 metal coat until a desired thickness is attained. The present
invention cantemplates various combinations of metal alloy layers
such as a single nick~Ilboran alley layer, a primary nickellboron
alloy layer followed by a secondary nickel/phosphorus layer or a
primary nickellboran alloy layer followed by a secondary copeer
2 5 layer and a tertiary cobalt layer.
An article of manufacture of the preferred embodiment
is an article such as metal alloy coated cubic boron nitride abrasive
particles embedded in a resinous matrix of an abrasive tool, such as
a grinding wheel, having particle surfaces electrolessly metal
3 0 coated with a first nickellboron alloy coat th~reon by the process of
the present invention. A second metal Bayer preferably of
nickellphosphorus may be disposed on top of the first metal coat,
the second layer being electrolessly or electrolytically applied on
the first layer. As stated earlier, the second layer is preferably
3 5 deposited by electroless metal deposition. The combined thickness
2a'~~2~4
-1 0 - RD-z1,493
of the metal layers is adjusted to a desired thickness sufficient to
withstand the abrading action.
Another example of an article of manufacture disclosed
in the present invention is an abrasive tool, such as an end mill,
having an abrasive surface provided by a metal alloy coated cubic
boron nitride film, typically a disc. The surfac~ of the film is
provided with an electrolessly plated nickel/boron alloy coat. A
second metal layer preferably of nickel/phosphorus may be disposed
on top of the first metal coat, the second layer being electrolessly
or electrolytically applied on the first layer. 8y providing the cubic
boron nitride film with such a metal alloy coat, its degree of
adhesion to another metal surface, such as the one provided by a tool
holder, is improved significantly.
The present invention will b~ further understood from
the illustration of specific examples which follow.
A z00 milliliter aqueous solution of Ni/B efectroless
bath was made by mixing 0.114 M nickel sulfate, 0.337M malic acid
z 0 and O.OSM dimethylamine borane. The pH of the bath was adjusted to
5.5 by using N~i~OH. The bath was maintained at 35~C during plating.
Several one inch diameter discs prepared from a
polycrystalline cubic boron nitride film were first activated by
placing them in a solution of MacDermid~ D34C Pd for 4 minutes at
z59C, followed by washing in deionized water and then by drying in
air.
Some of the cubic boron nitride discs were then placed in
the plating bath. Plating time was 10 minutes. A Ni/B coat of 1.0
micrometer thick was deposited on the discs. The discs were then
3 0 gradually heated in a non-oxidizing atmosphere of 7°/~ Hydrogen
93°/~
Argon at a rate of lO~Clminute to various heat treatment
temperatures, shown in Table 1 below. The heat treatment was
conducted for 1 hour.
~o~~z~~
-1 1 - R~-21,493
The adhesion was measured with a Sebastian Model I
adhesion tester, sold by Quad Group, Santa Barbara, California. The
adhesion tester measures the force in pounds per square inch (psi)
required to pull a standardized epoxy coated pin ofif the test surface.
The standardized epoxy coated pin is sold by Quad Group, Spokane,
Washington. The epoxy surface of the pin was held against the test
surface and then heated according to the standard test procedure to
allow the epoxy to set to a standard adhesion level. The standard
procedure specifies heating the pin with a test sample attached
1 0 thereto for one hour at 1500C. The adhesion forces required to
separate the Ni/B coating from the pin are tabulated in Table 1.
Table 1 Adhesion of Nill3 to C13N
1 5 Heat Treat Temperature (~C) Adhesion (psi)
500 250
550 1340
20 600 7000
600 8090
600 190
600 3830
625 ' S0
25 625 7280
625 1390
650 500
650 210
650 750
30 700 50
Tne Ni/~ Payer on the disc, when examined under scanning
electron microscopy, showed a smooth well wetted surface. The
3 5 NiIS coating was leached off the cubic boron nitride substrate and
analyzed by atomic . absorption spectroscopy to determine its
composition. The NI/Mo coating was found to have a composition of
4 % B, 96% Ni.
-1 2- RD-21,493
For comparison, one of the aforementioned cubic boron
nitride discs was nickel coated by a conventional AK1000~ Ni/P
bath without addition of boron. This coating showed complete
balling of the nickel coat from the cubic boron nitride surface after
the heat treatment and under the aforementioned adhesion test, this
coating separated from the cubic boron nitride surface of the disc at
less than 100 psi. Therefore, it is apparent that by alloying nickel
with boron, by the method of the present invention, an unexpectedly
significant improvement in adhesion of the nickel coat to the cubic
boron nitride is achieved.
A 20 gram batch of 170/200 mesh size ~orazon~ cubic
1 5 boron nitride powder, sold by GE Suparabrasives, Worthington, Ohio
was suspended in Mac~ermid~ D34C Pd catalyst for 4 minutes at
25~C, and than rinsed in daionized water and air dried. Tha cubic
boron nitride particles ware placed in 1500 ml of the Ni/~ bath
described in example 1. The cubic boron nitride powder was rinsed
in deionized water after electroless plating by the Nil bath and
than filtered and air dried. Tha alactrolassly plated cubic boron
nitride powder was than heat treated for one hour in 7°/~ Hydrogen
93% Argon. The heat was gradually increased at a steady rate of
lOaC/minute to s00oC. Tha heat treated cubic boron nitride powder
2 5 was then examined under scanning electron microscopy. Tha
examination showed cubic boron nitride powder particles having a
uniform well wetted coat. Tha Ni/~ coating was stripped off the
cubic boron nitride powder in a conventional acid bath and then
analyzed by atomic absorption spectroscopy for its composition.
3 0 The Ni/B composition was identical to the one in example 1. Tha
thickness of Ni/~ coat was calculated frorrs the weight gain,
assuming uniform coverage. It was determined to be 0.9
micrometers. The Nile coated cubic boron nitride particles ware
than electrolessly plated with a second layer in AK1000~ Ni/P bath
3 5 for a time sufficient to obtain 56% by weight of nickel. This cubic
boron nitride powder was than used in an abrasive grinding wheel.
-1 3- R~-21,493
The particles of the cubic boron nitride powder showed good
adhesion to the Ni/S bond coat and Ni/P overcoat.
A 200 milliliter solution of NilMo elactroiess bath was
made by adding 0.015 M sodium molybdata to a standard alectroless
AK1000~ Ni/P bath. The pH of the bath was adjusted to 9 by using
NaOH. Tha bath was maintained at 85pC during plating. An activated
cubic boron nitride disc, activated by the steps described in Exempla
1 0 1, was than placed in the plating bath. PBating time was 20 minutes.
The NlIMo coat on the cubic boron nitride disc was 2.0
micrometers thick. The disc sample was gradually heated in a non-
oxidizing atmosphere of 7°/~ Hydrogen 93% Argon at a rata of
9 OoClminuta to 900~C and then heat treated for 1 hour.
1 5 The adhesion was measured with the S~bastian Modal I
adhesion tester described in Exampia 1. Tha adhesion force required
to separate the Ni/Mo coating from the pin was in excess of 3700
psi. The coating was leached off the cubic boron nitride substrata
and analyzed by atomic absorption spectroscopy to determine its
20 composition. Tha Ni/Mo coating was found to have a composition of
15.8% Mo, 83.4% Ni, 0.8% P.
For comparison, one of the aforementioned cubic boron
nitride discs was nickel coated by a conventional AK1000~ Ni/P
bath without addition of Mo. This coatin~l showed complete balling
2 5 of the nickel coat from the cubic boron r9itride surfac~ after the heat
treatment and under the aforementioned adhesion test, this coating
separated from the cubic boron nitride surface of the disc at less
than 100 psi. Therefore, it is apparent that by aitoying nickel with
M~, by the method of th~ present invention, an unexpectedly
30 significant improvement in adhesion of the nickel coat to the cubic
boron nitride is achieved.
